US20150080276A1 - Phosphoric ester preparations with reduced hygroscopicity - Google Patents

Phosphoric ester preparations with reduced hygroscopicity Download PDF

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US20150080276A1
US20150080276A1 US14/481,035 US201414481035A US2015080276A1 US 20150080276 A1 US20150080276 A1 US 20150080276A1 US 201414481035 A US201414481035 A US 201414481035A US 2015080276 A1 US2015080276 A1 US 2015080276A1
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phosphoric ester
alkylene
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Jan-Gerd Hansel
Heiko Tebbe
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Lanxess Deutschland GmbH
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Publication of US20150080276A1 publication Critical patent/US20150080276A1/en
Priority to US16/177,714 priority Critical patent/US11193004B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/14—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
    • C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • C08G2101/0008—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/0405—Phosphate esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/66—Hydrolytic stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to phosphoric ester preparations with reduced hygroscopicity, to a method for production thereof and to use of these as flame retardants and hydraulic fluids, and also to polyurethanes which comprise the phosphoric ester preparations of the invention.
  • Poly(alkylene phosphates) can be used in various technical applications, for example as lubricants (cf. U.S. Pat. No. 2,632,767), hydraulic fluids (cf. U.S. Pat. No. 4,056,480), plasticizers (cf. U.S. Pat. No. 2,782,128) and as flame retardants (cf. EP 1 746 129 B1, and the European Patent Application No. 12177287.5 which is not a prior publication).
  • Hygroscopicity is the term used for the property that causes a substance to absorb water from the water vapour present in air. This process causes an uncontrolled rise in the water content of the poly(alkylene phosphates), and this can lead to difficulties in the applications mentioned: the increased water content in hydraulic fluids can lead to the formation of vapour bubbles which can cause undesired compressibility. Flame retardants with undesired water content can cause hydrolysis of the matrix that is to be protected (for example a plastic).
  • WO 2001/018088 A1 describes mixtures of oligomeric poly(alkylene phosphates) and non-oligomeric, non-halogenated organophosphorus flame retardants.
  • WO 2001/018088 A1 does not address the hygroscopicity problem.
  • WO 2001/018088 A1 gives particular preference to mixtures based on what is known as poly(ethyl ethyleneoxy) phosphate, EtO-[P( ⁇ O)OEt-CH 2 CH 2 —] n —P( ⁇ O)(OEt) 2 , where the average value of the number of the repeating units n is from 2 to 20.
  • Poly(ethyl ethyleneoxy)phosphate is marketed by way of example as Fyrol® PNX by ICL-IP. These mixtures based on poly(ethyl ethyleneoxy)phosphate are described in WO 2001/018088 A1 as flame retardants for polyurethane foams, but feature a considerable disadvantage: that they although they can be successfully processed with polyether polyols they cannot be successfully processed with polyester polyols (see Examples).
  • the said object is achieved via mixtures which comprise certain phosphoric esters alongside an oligomer mixture of poly(alkylene phosphates).
  • R 9 is a moiety of the formula —CH 2 —CH ⁇ CH—CH 2 —, a moiety of the formula —CH 2 —C ⁇ C—CH 2 —, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II)
  • poly(alkylene phosphates) of the formula (I) in which A is a moiety of the formula (II), in which R 10 and R 11 are identical and are methyl, or is a moiety of the formulae (V), (VI) or (VII),
  • poly(alkylene phosphates) of the formula (I) in which A is a moiety of the formula —CHR 5 —CHR 6 —(O—CHR 7 —CHR 8 ) a —, in which a is a number from 1 to 2 and R 5 , R 6 , R 7 and R 8 are identical and are H or is a moiety of the formula —(CHR 5 —CHR 6 —O) c —R 9 —(O—CHR 7 —CHR 8 ) d —, in which c and d are mutually independently an integer from 1 to 2, and R 9 is a moiety of the formula (II), where R 10 and R 11 are identical and are methyl.
  • phosphoric ester preparations of the invention which comprise an oligomer mixture a) comprising at least three poly(alkylene phosphates) of the formula (I),
  • phosphoric ester preparations of the invention which comprise an oligomer mixture a) comprising at least three poly(alkylene phosphates) of the formula (I)
  • phosphoric ester preparations of the invention which comprise an oligomer mixture a) comprising at least three poly(alkylene phosphates) of the formula (I)
  • the oligomer mixtures a) present in the phosphoric ester preparations of the invention and the poly(alkylene phosphates) present therein are halogen-free.
  • the expression “halogen-free” means that the poly(alkylene phosphates) of the formula (I) do not comprise the elements fluorine, chlorine, bromine and/or iodine and that the oligomer mixtures a) present in the phosphoric ester preparations of the invention do not comprise any other substances in a quantity that causes content of one or more of the elements fluorine, chlorine, bromine and iodine to be greater than 5000 ppm, based on the oligomer mixture a).
  • the oligomer mixtures a) present in the phosphoric ester preparations of the invention comprise at least three, preferably more than three different poly(alkylene phosphates) of the general formula (I) which differ from one another at least in the number n of the repeating units and thus in their molar mass.
  • the person skilled in the art uses suitable average values to describe oligomer mixtures of this type, for example the number-average molar mass M n and the average value of the number of the repeating units n in the molecules of the formula (I) present in the oligomer mixture.
  • the number-average molar mass M n of the poly(alkylene phosphates) of the formula (I) present in the oligomer mixture a) in the invention is determined via gel permeation chromatography with tetrahydrofuran as eluent against polystyrene standards. This method is known to the person skilled in the art, for example from DIN 55672-1:2007-08. From M n it is easily possible, by considering the stoichiometry of the formula (I), to calculate the average value of the number of the repeating units n in the poly(alkylene phosphates) present in the oligomer mixture a) (see Production Example).
  • the phosphoric esters b) present in the phosphoric ester preparations of the invention are preferably esters of orthophosphoric acid having identically or differently substituted alkyl, alkylene, alkoxyalkylene, arylalkyl, aryl, arylene or hetaryl moieties.
  • the materials can also be mixtures of various esters of the sort frequently encountered in technical products of this type.
  • the phosphoric esters b) are compounds of the formula (VIII)
  • the phosphoric esters b) are compounds of the formula (VIII)
  • Examples of the preferred phosphoric esters b) are triphenyl phosphate, diphenyl cresyl phosphate, tricresyl phosphate, isopropylated or butylated aryl phosphates, bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), hydroquinone bis(diphenyl phosphate), neopentyl glycol bis(diphenyl phosphate), triisobutyl phosphate, tributoxyethyl phosphate, tris(chloroisopropyl)phosphate and tris(dichloropropyl)phosphate and mixtures of these.
  • the phosphoric esters b) are commercially obtainable products or can be produced by a known method. It is also possible to use technical products as phosphoric esters b). It is preferable here to use those technical products which are termed “neutral” phosphoric esters, i,e. which have an acid number below 10 mg KOH/g, preferably below 5.0 mg KOH/g and particularly preferably below 2.0 mg KOH/g.
  • the oligomer mixtures a) can be produced via methods known to the person skilled in the art for the production of alkyl phosphates.
  • the oligomer mixtures a) can be produced via the reaction of alkyl dichlorophosphates of the formula MO—POCl 2 , in which M is a moiety R 1 , R 2 , R 3 or R 4 and R 1 , R 2 , R 3 and R 4 comply with the general and preferred definitions given above, with dihydroxy compounds of the formula HO-A-OH, in which A complies with the general and preferred definitions given above, and with one or more monohydroxy compounds M-OH, in which M is defined as above, or via reaction of dihydroxy compounds of the formula HO-A-OH, in which A complies with the general and preferred definitions given above, with phosphorus oxychloride POCl 3 and with one or more monohydroxy compounds M-OH, in which M is a moiety R 1 , R 2 , R 3 or R 4
  • the present invention further provides a process for the production of the phosphoric ester preparations of the invention, characterized in that an oligomer mixture a) complying with the general or preferred definition given above and at least one phosphoric ester b) complying with the general or preferred definition given above are mixed with one another.
  • the phosphoric ester preparation of the invention generally comprises from 30 to 70% by weight, preferably from 40 to 60% by weight, of oligomer mixture a) and from 30 to 70% by weight, preferably from 40 to 60% by weight, of at least one phosphoric ester b), based on the entire preparation.
  • the phosphoric ester preparations of the invention are liquid at about 23° C.
  • the viscosity of the phosphoric ester preparations of the invention is from 20 to 5000 mPas at 23° C. It is particularly preferable that the viscosity is from 20 to 1000 mPas at 23° C.
  • the phosphoric ester preparations of the invention can preferably comprise, alongside components a) and b), as required by application sector, one or more auxiliaries, for example from the group of the solvents, antioxidants, stabilizers and colorants.
  • auxiliaries for example from the group of the solvents, antioxidants, stabilizers and colorants. Examples of these auxiliaries that can be used are:
  • the phosphoric ester preparations of the invention are suitable for use as flame retardants and for the production of flame retardant preparations.
  • the present invention further provides the use of the phosphoric ester preparations of the invention as flame retardants.
  • the phosphoric esters preparations can be used as flame retardants in any of the applications known to the person skilled in the art for flame retardants. It is preferable that the phosphoric ester preparation of the invention is used as flame retardant for
  • the phosphoric ester preparations of the invention are used as flame retardants for polyurethanes. It is very particularly preferable that the phosphoric ester preparations are used as flame retardants for polyurethane foams.
  • the polyurethane foams are flexible polyurethane foams or rigid polyurethane foams. It is preferable that the phosphoric ester preparations are used as flame retardants for flexible polyurethane foams which are produced from polyether polyols, i.e. flexible polyether-polyurethane foams. In an alternative, likewise preferred, embodiment of the invention the phosphoric ester preparations are used as flame retardants for flexible polyurethane foams which are produced from polyester polyols, i.e. flexible polyester-polyurethane foams.
  • the present invention further provides polyurethanes which comprise at least one phosphoric ester preparation of the invention. These polyurethanes can be produced in flame-retardant form via suitable selection of the quantity of phosphoric ester preparations present.
  • the flame-retardant polyurethanes of the invention can be produced by reacting organic polyisocyanates with compounds having at least two hydrogen atoms reactive towards isocyanates with conventional blowing agents, stabilizers, activators and/or other conventional auxiliaries and additives in the presence of at least one phosphoric ester preparation of the invention.
  • the quantity used of the phosphoric ester preparations of the invention is from 0.5 to 30 parts by weight, preferably from 3 to 25 parts by weight, based on 100 parts by weight polyol component.
  • the polyurethanes are isocyanate-based polymers which mainly have urethane groups and/or isocyanurate groups and/or allophanate groups and/or uretdione groups and/or urea groups and/or carbodiimide groups.
  • the production of isocyanate-based polymers is known per se and is described by way of example in German Offenlegungschrift 16 94 142, 16 94 215 and 17 20 768, and also in Kunststoff-Handbuch [Plastics handbook] Volume VII, Polyurethane [Polyurethanes], edited by G. Oertel, Carl-Hanser-Verlag Kunststoff, Vienna 1993.
  • the flame-retardant polyurethanes of the invention are thermoset polyurethanes, polyurethane foams, polyurethane elastomers, thermoplastic polyurethanes, polyurethane coatings and polyurethane lacquers, polyurethane adhesives and polyurethane binders or polyurethane fibres.
  • the flame-retardant polyurethanes of the invention are flame-retardant polyurethane foams.
  • Polyurethane foams are broadly divided into flexible and rigid foams. Although flexible and rigid foams can in principle have approximately the same envelope density and the same composition, flexible polyurethane foams have only little crosslinking and exhibit only low resistance to deformation under pressure. In contrast to this, the structure of rigid polyurethane foams is composed of highly crosslinked units and rigid polyurethane foam exhibits very high resistance to deformation under pressure. Typical rigid polyurethane foam has closed cells and has low thermal conductivity. Primary factors influencing the subsequent foam structure and foam properties during the production of polyurethanes via reaction of polyols with isocyanates are the structure and molar mass of the polyol, and the reactivity and number (functionality) of hydroxy groups present in the polyol.
  • Preferred envelope densities of the polyurethane foams of the invention are from 10 to 150 kg/m 3 . They particularly preferably have envelope densities of from 20 to 50 kg/m 3 .
  • Q is an aliphatic hydrocarbon moiety having from 2 to 18, preferably from 6 to 10, C atoms, a cycloaliphatic hydrocarbon moiety having from 4 to 15, preferably from 5 to 10, C atoms, an aromatic hydrocarbon moiety having from 6 to 15, preferably from 6 to 13, C atoms or an araliphatic hydrocarbon moiety having from 8 to
  • polyisocyanates that derive from tolylene 2,4- and/or 2,6-diisocyanate or from diphenylmethane 4,4′- and/or 2,4′-diisocyanate, these being readily obtainable in industry.
  • polyol component Compounds having at least two hydrogen atoms reactive towards isocyanates with molar mass from 400 to 8000 g/mol.
  • polyol component Compounds having at least two hydrogen atoms reactive towards isocyanates with molar mass from 400 to 8000 g/mol.
  • polyol component Compounds having at least two hydrogen atoms reactive towards isocyanates with molar mass from 400 to 8000 g/mol.
  • the polyols are polyethers and polyesters, and also polycarbonates and polyesteramides, these being known per se for the production of homogeneous and of cellular polyurethanes, being described for example in German Offenlegungschrift 28 32 253. Preference is given in the invention to the polyesters and polyethers having at least two hydroxy groups.
  • the polyurethane foams of the invention can therefore be produced in the form of rigid or flexible foams via appropriate selection, easily found in the prior art, of the starting materials.
  • Other optional starting components are compounds having at least two hydrogen atoms reactive towards isocyanates and molar mass from 32 to 399 g/mol. Again here these are compounds having hydroxy groups and/or amino groups and/or thiol groups and/or carboxy groups, preferably compounds having hydroxy groups and/or amino groups, where said compounds serve as chain extenders or crosslinking agents. These compounds generally have from 2 to 8, preferably from 2 to 4 hydrogen atoms reactive towards isocyanates. Examples of these are likewise described in German Offenlegungschrift 28 32 253.
  • blowing agent e.g. n-pentane, isopentane, cyclopentane, acetone, halogenated alkanes, such as trichloromethane, methylene chloride or chlorofluoroalkanes, CO 2 and others.
  • auxiliaries and additions such as catalysts of the type known per se, surface-active additives such as emulsifiers and foam stabilizers, reaction retarders, e.g. acidic substances such as hydrochloric acid or organic acyl halides, and also cell regulators of the type known per se, for example paraffins or fatty alcohols and dimethylpolysiloxanes, and also pigments or dyes and other flame retardants, stabilizers to counter effects of ageing and of weathering, core-discoloration inhibitors, plasticizers and fungistatic and bacteriostatic substances, and also fillers such as barium sulphate, kieselguhr, carbon black or purified chalk (German Offenlegungschrift 27 32 292).
  • surface-active additives such as emulsifiers and foam stabilizers
  • reaction retarders e.g. acidic substances such as hydrochloric acid or organic acyl halides
  • cell regulators of the type known per se, for example paraffins or fatty alcohols and
  • Particular core-discoloration inhibitors that can be present are sterically hindered trialkylphenols, alkyl esters of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, benzofuran-2-ones, secondary aromatic amines, phosphites, phenothiazines or tocopherols.
  • the present invention further provides a process for the production of polyurethanes via reaction of organic polyisocyanates with compounds having at least two hydrogen atoms reactive towards isocyanates and conventional blowing agents, stabilizers, catalysts, activators and/or other conventional auxiliaries and additives at from 20 to 80° C., by using a quantity of from 0.5 to 30 parts by weight, based on 100 parts by weight of polyol component, of at least one phosphoric ester preparation of the invention. It is preferable that the quantity used of the phosphoric ester preparations is from 3 to 25 parts by weight, based on 100 parts by weight of polyol component.
  • the process for the production of polyurethanes of the invention is carried out by reacting the reaction components described above in the single-stage process known per se, in the prepolymer process or in the semiprepolymer process, often with use of machinery such as that described in U.S. Pat. No. 2,764,565. Details concerning processing equipment which can also be used in the invention are described in Kunststoff-Handbuch [Plastics Handbook] Volume VII, Polyurethane [Polyurethanes], edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff, Vienna 1993, pp. 139 to 192.
  • the process of the invention can also produce cold-curing foams (GB Patent 11 62 517, German Offenlegungschrift 21 53 086). However, it is also of course possible to produce foams via block foaming or by the twin-belt process known per se. Polyisocyanurate foams are produced by using the processes and conditions known for that purpose.
  • the process of the invention permits the production of polyurethane foams in the form of rigid or flexible foams continuously or batchwise, or in the form of foam mouldings. Preference is given to the process of the invention in the production of flexible foams produced via a block foaming process.
  • the polyurethanes obtainable in the invention are preferably used in furniture cushioning, textile inlays, mattresses, vehicle seats, armrests, components, seat cladding and dashboard cladding, cable sheathing, gaskets, coatings, lacquers, adhesives, adhesion promoters and fibres.
  • the present invention provides the use of the phosphoric ester preparations of the invention as hydraulic fluids or for the production of hydraulic fluids. It is preferable that the phosphoric ester preparations are used in flame-retardant hydraulic fluids.
  • the phosphoric ester preparations of the invention can be produced from known components by known methods.
  • the liquid phosphoric ester preparations are easy to meter and are therefore very easy to process.
  • the number-average molar mass M n of the oligomer mixture was determined via GPC with tetrahydrofuran as eluent against polystyrene standards by a method based on that of DIN 55672-1:2007-08.
  • the average value of the number of repeating units n in the poly(alkylene phosphates) corresponding to the formula (I) present in the oligomer mixture was calculated in accordance with the following formula from the number-average molar mass M n measured:
  • n ( M n ⁇ M E )/ M R
  • the oligomer mixture a) produced in accordance with the above specification was used for the Examples. Water absorption was determined on the pure oligomer mixture a) (Comparative Example M-CE1), and also on mixtures of 50% by weight of oligomer mixture a) and 50% by weight of phosphoric ester b) according to Table 1. All of the phosphoric esters listed in Table 1 were commercially obtainable products with acid number ⁇ 0.1 mg KOH/g. For determination of water absorption, 100 ml of each mixture to be tested were charged to a 250 ml glass beaker (height 12 cm, diameter 6 cm) and placed, uncovered, for 7 days in a chamber under controlled climatic conditions at 23° C. and 50% relative humidity. The water content of the mixtures was determined by means of Karl-Fischer titration in accordance with DIN 51777. Each of the samples was homogenized by stirring before the water determination.
  • the phosphoric ester preparations M-IE1 to M-IE8 of the invention exhibit markedly lower water absorption than the oligomer mixture a) alone. They therefore feature reduced hygroscopicity, and this is an advantage in water-sensitive industrial applications.
  • the mixture M-CE2 not of the invention, made of the oligomer mixture a) and of the phosphoric ester triethyl phosphate with water solubility of more than 3.0 g/l at 25° C. absorbs markedly more water than the oligomer mixture a) alone, and therefore has markedly poorer suitability for water-sensitive industrial applications.
  • Table 3 states the raw materials for the production of flexible polyether-polyurethane foams.
  • the diisocyanate was then added and incorporated by brief vigorous stirring. After a cream time of from 15 to 20 s and a full rise time of from 170 to 200 s, a flexible polyether-polyurethane foam was obtained with envelope density 33 kg/m 3 . Uniformly fine-pored foams were obtained in all of the Examples.
  • the flexible polyurethane foams (polyether and polyester) were tested in accordance with the specifications of the Federal Motor Vehicle Safety Standards FMVSS 302 and allocated to the fire classes SE (self-extinguishing), SE/NBR (self-extinguishing/no burning rate), SE/BR (self-extinguishing/with burning rate), BR (burning rate) and RB (rapid-burning).
  • SE self-extinguishing
  • SE/NBR self-extinguishing/no burning rate
  • SE/BR self-extinguishing/with burning rate
  • BR burning rate
  • RB rapid-burning
  • Examples IE1 and IE2 show that the phosphoric ester preparations of the invention with reduced hygroscopicity exhibit the same flame-retardant effect as the known hygroscopic oligomer mixtures a) alone.
  • Table 5 states the raw materials for the production of flexible polyester-polyurethane foams.
  • the two premixed diisocyanates were then added and incorporated by brief vigorous stirring.
  • a cream time of from 10 to 15 s and a full rise time of from 70 to 80 s a flexible polyester-polyurethane foam was obtained with envelope density 29 kg/m 3 .
  • the foam structure of the flexible polyester-polyurethane foams was dependent on the flame retardants used. It is recorded in Table 6 as “uniformly fine-pored” (“uf”) or “non-uniformly coarse-pored” (“nc”).
  • a mixture described in WO 2001/018088 A1, made of an oligomer mixture of poly(alkylene phosphate) of the formula EtO-[P( ⁇ O)OEt-CH 2 CH 2 —] n —P( ⁇ O)(OEt) 2 (M-CE3; CAS Reg. No. 184538-58-7, average value of the number of repeating units n 3.01) and RDP in a ratio by mass of 1:1 cannot be successfully processed to give a flexible polyester-polyurethane foam (Comparative Example CE4).
  • the foam is non-uniformly coarse-pored and thus unusable. This shows that the mixture M-CE3 from the prior art is not compatible with polyester polyols.
  • the phosphoric ester preparations of the invention permit the production of foams with the desired, uniformly fine-pored foam structure.
  • Inventive Example IE4 uses the phosphoric ester preparation M-IE5 of the invention which, like M-CE3, comprises 50% by weight of RDP as phosphoric ester b), and is therefore directly comparable with Comparative Example CE4.
  • the foams from Inventive Examples IE3 and IE4 achieve the best MVSS fire class SE (self-extinguishing) with 6 parts of flame retardant.
  • Examples IE3 and IE4 show that the phosphoric ester preparations of the invention with reduced hygroscopicity have good processability with polyester polyols and exhibit the same flame-retardant effect as the known hygroscopic oligomer mixtures a) alone.

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